The present invention generally relates to detergent compositions, and more particularly, to detergent compositions which have a plasma-induced, water-soluble coating. The detergent compositions may be used in laundry, dishwashing, carwashing, hard surface cleaning or other similar applications. The plasma-induced, water-soluble coating controls the solubility, dispersion, flowability and chemical stability of the detergent composition. The invention also provides a process for making such detergent compositions.
Currently, detergent formulators are faced with numerous problems which impede delivering the active ingredients to the fabric or dishware to be cleaned. By way of example, recent low dosage or xe2x80x9ccompactxe2x80x9d detergent products experience dissolution problems, especially in cold temperature laundering solutions (i.e., less than about 30xc2x0 C.). More specifically, poor dissolution results in the formation of xe2x80x9cclumpsxe2x80x9d which appear as solid white masses remaining in the washing machine or on the laundered clothes after conventional washing cycles. These xe2x80x9cclumpsxe2x80x9d are especially prevalent under cold temperature washing conditions and/or when the order of addition to the washing machine is laundry detergent first, clothes second and water last (commonly known as the xe2x80x9cReverse Order Of Additionxe2x80x9d or xe2x80x9cROOAxe2x80x9d). Similarly, this clumping phenomenon can contribute to the incomplete dispensing of detergent in washing machines equipped with dispenser drawers or in other dispensing devices, such as a granulette. In this case, the undesired result is undissolved detergent residue in the dispensing device.
Another similar problem with detergent compositions, especially granular laundry and dishwashing detergents, is the degradation of physical properties over extended storage periods. More particularly, spray dried granules and other particulate detergent ingredients have a tendency to xe2x80x9ccakexe2x80x9d while stored in the detergent box, especially under highly humid conditions. Such xe2x80x9ccakingxe2x80x9d is very unacceptable to consumers and can lead to difficulties in xe2x80x9cscoopingxe2x80x9d or otherwise removing the detergent from the box in which it is contained. This problem can also result in improper dosing of the laundering solution resulting in decreased cleaning performance. Other problems include chemical instability of the detergent composition and difficulty in dispersing polymers into wash solutions. Heretofore, detergent formulators have unsuccessfully attempted to resolve or minimize all of the aforementioned problems, and they continue to search for convenient solutions which do not affect other properties of the detergent composition.
Accordingly, despite the above disclosures in the art, there is a need for detergent compositions which have improved physical properties, solubility and/or chemical stability. There is also a need for a process for producing such detergent compositions.
The invention meets the above-identified needs by providing a detergent composition having a plasma-induced, water-soluble coating for controlling solubility, chemical stability and physical properties. The invention also provides a process for making such a detergent composition involving subjecting a detergent material to a plasma glow zone in which an organic hydrophilic monomer is introduced such that it ultimately deposits on the detergent material to form a water soluble coating. The detergent compositions are particulate or non-particulate (e.g., tablet) and can be used for laundry, dishwashing or other similar application.
In accordance with one aspect of the invention, a detergent composition is provided. The detergent composition comprises particulate material containing a detergent ingredient selected from the group consisting of detersive surfactants, builders and mixtures thereof; wherein at least a portion of the particulate material has a plasma-induced, water-soluble coating. In accordance with another aspect of the invention, the detergent composition comprises a non-particulate material containing a detergent ingredient selected from the group consisting of detersive surfactants, builders and mixtures thereof; wherein at least a portion of the non-particulate material has a plasma-induced, water-soluble coating.
In accordance with yet another aspect of the invention, a process for producing a detergent composition is provided. The process comprises the steps of: (a) providing a detergent material containing a detergent ingredient selected from the group consisting of detersive surfactants, builders and mixtures thereof; (b) subjecting the detergent material to plasma glow zone in which a gas is ionized and an organic hydrophilic monomer is introduced such that the organic hydrophilic monomer deposits on the detergent material to form a water-soluble coating. As used herein, the xe2x80x9cplasma glow zonexe2x80x9d is the space or region where plasma is generated using electricity, such as the space between two electrodes in a plasma vacuum chamber.
All percentages, ratios and proportions used herein are by weight, unless otherwise indicated. All documents including patents and publications cited herein are incorporated herein by reference.
Accordingly, it is an advantage of the invention to provide a detergent composition which has improved physical properties, solubility and/or chemical stability. It is also an advantage of the invention to provide a process for producing such detergent compositions in an convenient manner. These and other advantages and features of the present invention will become apparent to those skilled in the art from a reading of the following detailed description of the preferred embodiments and the appended claims.
In essence, the invention is directed to particulate and non-particulate detergent compositions having a plasma-induced, water-soluble coating. In preferred modes of the invention, the particulate material is selected from spray dried granules, agglomerates and mixtures thereof, and is applied in the laundry, dishwashing or similar context. The non-particulate detergent compositions herein may also be applied to laundry or dishwashing, for example, as a laundry or dishwashing tablet, block, cylinder, cube, sheet or other non-particulate configuration.
Preferably, the water-soluble coating is formed from an organic hydrophilic monomer, which is even more preferably selected from the group consisting of acrylates, methacrylates, acrylamides, methacrylamides, maleates, fumarates, vinyl ethers and mixtures thereof. More preferably, the organic monomer is selected from the group consisting of 2-hydroxyethyl methacrylate, N,N-dimethylacrylamide, acrylic acid, methacrylic acid and mixtures thereof. Most preferably, the organic monomer is acrylic acid.
The water-soluble coating is on at least a portion of the detergent compositions described herein. By xe2x80x9cat least a portionxe2x80x9d, it is meant that at least 1%, preferably 90% to 100% of the particulate or non-particulate detergent composition has a water-soluble coating on it. It should be understood that not all of the detergent composition needs to be coated to be within the scope of the invention. To that end, a plasma coating process is used to place the water-soluble coating on the detergent composition. As detailed hereinafter, this is accomplished by ionizing a gas, such as argon, using high frequency electricity in a plasma vacuum chamber. Suitable gases may be selected from the group consisting of argon, helium, oxygen, nitrogen and mixtures thereof
Typical plasma chambers will have a xe2x80x9cplasma glow zonexe2x80x9d which can be the region between the two electrodes used to generate the high frequency electricity, and thus the plasma therebetween. The plasma chamber can be embodied in a fluidized bed dryer or cooler, tumbling drum, vibrating conveyor belt or other similar apparatus used in the commercial scale production of particulate detergent compositions. The pressure inside the plasma chamber is typically maintained at a pressure of from about 5 mTorr to about 300 Torr, preferably from about 10 mTorr to about 1 Torr, and most preferably from about about 50 mTorr to about 250 mTorr. The power used in the plasma coating is preferably from about 0.1 Watts to about 500 Watts, more preferably from about 0.5 Watts to about 100 Watts, and most preferably from about 1 Watt to about 10 Watts. In this way, the plasma coating process can be controlled so as not to destroy the functional attributes of the coating or the particulate material being plasma coated in accordance with the invention.
As used herein, the phrase xe2x80x9cplasma-inducedxe2x80x9d means that which has been deposited, coated or otherwise layered using one or more of plasma deposition techniques which should be contrasted with simple spraying techniques that do not employ gas ionized with electricity. This application of a high frequency electric field to a gas to form a plasma of gas ions is a known technique used in polymerization of monomers such as organic hydrophilic monomers which are suitable for use herein to form the water-soluble coating on the detergent composition. This technique has been described, for example, in Luster, U.S. Pat. No. 2,257,177. In general, this involves continuous contact of the polymerizing monomer in the vapor phase with the gas plasma until substantial completion of the graft polymerization on the substrate. This technique tends to form a cross-linked product as suggested by U.S. Pat. No. 3,287,242. Due to the high cross-linking associated with plasma polymerization, that technique is generally employed for the purpose of forming water-insoluble thin films or coatings rather than water-soluble coatings as currently contemplated by the invention. The activation is confined to a region near the surface of the substrate at which links and cross-links are formed.
One modification of the film/coating forming techniques in which the monomer is polymerized directly from the gas state is described in Knox et al, U.S. Pat. No. 3,475,307. There, the substrate is cooled to condense a thin layer of liquid monomer on the substrate in order to increase the polymerization rate. However, in that technique, the ordinary skilled artisan must avoid condensing xe2x80x9ctoo muchxe2x80x9d of the monomer on the surface because otherwise the incoming activated molecules from the gas phase would not reach the monomer removed from the gas liquid interface which is stated to cause a coating of little adherence (col. 10, lines 54-60). The order of magnitude of condensed monomer prior to polymerization is indicated as being few molecules in thickness (col. 4, lines 1-4).
Another plasma coating technique is to initiate polymerization by use of a non-equilibrium ionized gas plasma and to complete the majority of the polymerization in the absence of the plasma. In this manner, a high molecular weight polymer is formed. The formation of the ionized gas plasma may be accomplished in any of the techniques known to produce such plasmas. For example, see J. R. Hollahan and A. T. Bell, eds., xe2x80x9cTechniques in Applications of Plasma Chemistryxe2x80x9d, Wiley, New York, 1974 and M Shen, ed. xe2x80x9cPlasma Chemistry of Polymersxe2x80x9d, Marcel Dekker, New York, 1976. In one technique, an ionizable gas is contained under vacuum between parallel plate electrodes connected to a radio frequency generator which is sold by International Plasma Corporation under the designation xe2x80x9cModel 3001xe2x80x9d. The plasma can be created with such parallel plates either external or internal to the plasma chamber. In another technique, an external induction coil creates an electric field which produces the plasma of ionized gas. In yet another technique, oppositely charged electrode points are placed directly into the plasma vacuum chamber in spaced apart relationship to create the plasma. Any plasma formed by these techniques or any other one in which an electric field creates a path of electrical conduction totally within the gas phase is suitable for use in the invention.
As used herein, the term xe2x80x9cplasmaxe2x80x9d is to be distinguished from any liquid or solid environment in which an electric field is applied to create ions in a path through the solid or liquid. This is not to exclude the possibility that an electric field would also be applied across the non-vapor monomer. However, if it were, it is not believed that it would have any beneficial function; instead, it would be extraneous to the vapor phase plasma. The operating parameters for the plasma vary from monomer to monomer. In general, it is preferable to employ reduced gas pressures to form a glow discharge by electron liberation which causes ionization in the gas phase. Where a plasma is created in a chamber including a monomer gas at a pressure below atmospheric pressure, the plasma is formed when the interelectrode potential exceeds a threshold value which is sufficient to ionize or xe2x80x9cbreakdownxe2x80x9d the gas. This is a function of the composition of the gas, its pressure and the distance between the electrodes. After breakdown, the gas is conductive and a stable plasma may be maintained over a wide range of currents. Although the exact composition of the plasma is not known, it is believed to include electrons, ions, free radicals, and other reactive species.
The free radicals and/or ions in the plasma may be supplied by collision of plasma electrons with monomer vaporized from the non-vapor monomer to be polymerized. The monomer may be in the form of a liquid, a solid, or a solid-liquid mixture. For the liquid monomer, the monomer vapor is supplied by evaporation of monomer into the plasma which is facilitated by the application of a vacuum. Similarly, for the solid monomer, such free radicals and/or ions are supplied by sublimed monomer vapor. For simplicity of description, the non-vapor monomer to be activated will be described herein as being in the liquid state unless otherwise specified.
In a related procedure, the creation of active sites in the monomer may be facilitated by direct activation from the ionized gas, itself, in the plasma. For this purpose, the presence of any ionizable gas under the conditions prevalent in the plasma may be employed. For example, water vapor may be ionized to create active polymerization sites for certain monomers. Other gases which have been ionized by such plasmas include hydrogen chloride, carbon tetrachloride, and inert gases such as helium or neon. Those gases which are ionizable in the plasma are well known to those in the field. The monomer to be activated may be in the essentially pure monomeric state or in solution. In the latter instance, organic or inorganic solvents capable of complete dissolution of the monomer may be employed. Typical organic solvents for certain monomers include benzene and acetone. When a glow-discharge type of plasma is employed, excess vaporization of monomer may interfere with the plasma. Thus, when a pure normally liquid monomer of relatively high vapor pressure is employed, it is desirable to reduce its vapor pressure. For example, the monomer may be frozen to a solid form for plasma initiation in that state or warned to a mixed solid-liquid state prior to plasma initiation.
For any given plasma deposition technique as described herein, the process may involve the use of high frequency microwaves to ionize the gas in the plasma chamber. Alternatively, high frequency radio waves or direct current electricity can be used, for example to ionize the gas between two oppositely charged electrode points used to define the plasma glow zone in a plasma vacuum chamber. Another option is to pulsate or otherwise intermittently ionize the gas in the plasma glow zone in the plasma chamber so as to control the plasma-induced deposition of the monomer onto the particulate detergent material. Further control of plasma-induced deposition can be achieved in the process of the present invention by positioning the particulate detergent material to be coated with the hydrophilic monomer outside of the plasma glow zone. Alternatively or additionally, the water-soluble hydrophilic monomer may be introduced outside of the plasma glow zone, as well, to provide further control of the deposition.
As mentioned previously, the water-soluble coating is formed from an organic hydrophilic monomer, some of which are mentioned above. The detergent compositions preferably contain an effective amount of such monomer so as to achieve the desired solubility, flowability and/or chemical stability of the particulate or non-particulate composition. In typical formulations, the coating which is formed of the monomer grafted onto the particulate or non-particulate composition will have a thickness in the range of from about 0.001 microns to about 1000 microns, more preferably from about 0.05 microns to about 50 microns and most preferably from about 0.01 microns to about 10 microns.
Suitable organic hydrophilic monomers include generally water soluble conventional vinyl monomers such as: acrylates and methacrylates of the general structure 
where R2 is hydrogen or methyl and R3 is hydrogen or is an aliphatic hydrocarbon group of up to about 10 carbon atoms substituted by one or more water solublizing groups such as carboxy, hydroxy, amino, lower alkylamino, lower dialkylamino, a polyethylene oxide group with from 2 to about 100 repeating units, or substituted by one or more sulfate, phosphate, sulfonate, phosphonate, carboxamido, sulfonamido or phosphonamido groups, or mixtures thereof;
acrylamides and methyacrylamides of the formula 
where R2 and R3 are as defined above;
acrylamides and methyacrylamides of the formula 
where R4 is lower alkyl of 1 to 3 carbon atoms and R2 is as defined above;
maleates and fumarates of the formula
R3OOCHxe2x95x90CHxe2x80x94COOR3
wherein R3 is as defined above;
vinyl ethers of the formula
H2Cxe2x95x90CHxe2x80x94Oxe2x80x94R3
where R3 is as defined above;
aliphatic vinyl compounds of the formula
R2CHxe2x80x94CHR3
where R2 is as defined above and R3 is as defined above with the proviso that R3 is other than hydrogen; and vinyl substituted heterocycles, such as vinyl pyridines, piperidines and imidazoles and N-vinyl lactams, such as N-vinyl-2-pyrrolidone.
Included among the useful water-soluble monomers are: 2-hydroxyethyl-, 2- and 3-hydroxypropyl-, 2,3-dihydroxypropyl-, polyethoxyethyl-, and polyethoxypropyl acrylates, methacrylates, acrylamides and methacrylamides; acrylamide, methacrylamide, N-methylacrylamide, N-methylmethacrylamide, N,N-dimethylacrylamide, N, N-dimethylnethacrylamide; N,N-dimethyl- and N,N-diethyl-aminoethyl acrylate and methacrylate and the corresponding acrylamides and methacrylamides; 2- and 4-vinylpyridine; 4- and 2-methyl-5-vinylpyridine; N-methyl4-vinylpiperidine; 2-methyl-1-vinylimidazole; N,N-dimethylallyalamine; dimethylaminoethyl vinyl ether, N-vinylpyrrolidone; acrylic and methacrylic acid; itaconic, crotonic, fumaric and maleic acids and the lower hydroxyalkyl mono and diesters thereof, such as the 2-hydroxyethyl fumarate and maleate, sodium acrylate and methacrylate; maleic anhydride; 2-methacryloyloxyethylsulfonic acid and allylsulfonic acid.
Preferred water soluble monomers include 2-hydroxyethylmethacrylate; N, N-dimethylacrylamide; acrylic acid and methacrylic acid; and most preferably 2-hydroxyethyl methacrylate.
The particulate and non-particulate detergent compositions described herein preferably contain a detersive surfactant and a detergent builder, and optionally, a variety of common detergent ingredients. The surfactant system of the detergent composition may include anionic, nonionic, zwitterionic, ampholytic and cationic classes and compatible mixtures thereof. Detergent surfactants are described in U.S. Pat. No. 3,664,961, Norris, issued May 23, 1972, and in U.S. Pat. No. 3,919,678, Laughlin et al., issued Dec. 30, 1975, both of which are incorporated herein by reference. Cationic surfactants include those described in U.S. Pat. No. 4,222,905, Cockrell, issued Sep. 16, 1980, and in U.S. Pat. No. 4,239,659, Murphy, issued Dec. 16, 1980, both of which are also incorporated herein by reference.
Nonlimiting examples of surfactant systems include the conventional C11-C18 alkyl benzene sulfonates (xe2x80x9cLASxe2x80x9d) and primary, branched-chain and random C10-C20 alkyl sulfates (xe2x80x9cASxe2x80x9d), the C10-C18 secondary (2,3) alkyl sulfates of the formula CH3(CH2)x(CHOSO3xe2x88x92M+) CH3 and CH3 (CH2)y(CHOSO3xe2x88x92M+) CH2CH3 where x and (y+1) are integers of at least about 7, preferably at least about 9, and M is a water-solubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate, the C10-C18 alkyl alkoxy sulfates (xe2x80x9cAExSxe2x80x9d; especially EO 1-7 ethoxy sulfates), C10 -C18 alkyl alkoxy carboxylates (especially the EO 1-5 ethoxycarboxylates), the C10-18 glycerol ethers, the C10-C18 alkyl polyglycosides and their corresponding sulfated polyglycosides, and C12-C18 alpha-sulfonated fatty acid esters. If desired, the conventional nonionic and amphoteric surfactants such as the C12-C18 alkyl ethoxylates (xe2x80x9cAExe2x80x9d) including the so-called narrow peaked alkyl ethoxylates and C6-C12 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), C12-C18 betaines and sulfobetaines (xe2x80x9csultainesxe2x80x9d), C10-C18 amine oxides, and the like, can also be included in the surfactant system. The C10-C18 N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the C12-C18 N-methylglucamides. See WO 9,206,154. Other sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C10-C18 N-(3-methoxypropyl) glucamide. The N-propyl through N-hexyl C12-C18 glucamides can be used for low sudsing. C10-C20 conventional soaps may also be used. If high sudsing is desired, the branched-chain C10-C16 soaps may be used. Mixtures of anionic and nonionic surfactants are especially useful. Other conventional useful surfactants are listed in standard texts.
The detergent composition can, and preferably does, include a detergent builder. Builders are generally selected from the various water-soluble, alkali metal, ammonium or substituted ammonium phosphates, polyphosphates, phosphonates, polyphosphonates, carbonates, silicates, borates, polyhydroxy sulfonates, polyacetates, carboxylates, and polycarboxylates. Preferred are the alkali metal, especially sodium, salts of the above. Preferred for use herein are the phosphates, carbonates, silicates, C10-C18 fatty acids, polycarboxylates, and mixtures thereof. More preferred are sodium tripolyphosphate, tetrasodium pyrophosphate, citrate, tartrate mono- and di-succinates, sodium silicate, and mixtures thereof (see below).
Specific examples of inorganic phosphate builders are sodium and potassium tripolyphosphate, pyrophosphate, polymeric metaphosphate having a degree of polymerization of from about 6 to 21, and orthophosphates. Examples of polyphosphonate builders are the sodium and potassium salts of ethylene diphosphonic acid, the sodium and potassium salts of ethane 1-hydroxy-1, 1-diphosphonic acid and the sodium and potassium salts of ethane, 1,1,2-triphosphonic acid. Other phosphorus builder compounds are disclosed in U.S. Pat. Nos. 3,159,581; 3,213,030; 3,422,021; 3,422,137; 3,400,176 and 3,400,148, all of which are incorporated herein by reference.
Examples of nonphosphorus, inorganic builders are sodium and potassium carbonate, bicarbonate, sesquicarbonate, tetraborate decahydrate, and silicates having a weight ratio of SiO2 to alkali metal oxide of from about 0.5 to about 4.0, preferably from about 1.0 to about 2.4. Water-soluble, nonphosphorus organic builders useful herein include the various alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates and polyhydroxy sulfonates. Examples of polyacetate and polycarboxylate builders are the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylene diarnine tetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, and citric acid.
Polymeric polycarboxylate builders are set forth in U.S. Pat. No. 3,308,067, Diehl, issued Mar. 7, 1967, the disclosure of which is incorporated herein by reference. Such materials include the water-soluble salts of homo- and copolymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid and methylenemalonic acid. Some of these materials are useful as the water-soluble anionic polymer as hereinafter described, but only if in intimate admixture with the nonsoap anionic surfactant.
Other suitable polycarboxylates for use herein are the polyacetal carboxylates described in U.S. Pat. No. 4,144,226, issued Mar. 13, 1979 to Crutchfield et al., and U.S. Pat. No. 4,246,495, issued Mar. 27, 1979 to Crutchfield et al., both of which are incorporated herein by reference. These polyacetal carboxylates can be prepared by bringing together under polymerization conditions an ester of glyoxylic acid and a polymerization initiator. The resulting polyacetal carboxylate ester is then attached to chemically stable end groups to stabilize the polyacetal carboxylate against rapid depolymerization in alkaline solution, converted to the corresponding salt, and added to a detergent composition. Particularly preferred polycarboxylate builders are the ether carboxylate builder compositions comprising a combination of tartrate monosuccinate and tartrate disuccinate described in U.S. Pat. No. 4,663,071, Bush et al., issued May 5, 1987, the disclosure of which is incorporated herein by reference.
Water-soluble silicate solids represented by the formula SiO2.M2O, M being an alkali metal, and having a SiO2:M2O weight ratio of from about 0.5 to about 4.0, are useful salts in the detergent granules of the invention at levels of from about 2% to about 15% on an anhydrous weight basis, preferably from about 3% to about 8%. Anhydrous or hydrated particulate silicate can be utilized, as well.
Any number of additional ingredients can also be included as components in the granular detergent composition. These include other detergency builders, bleaches, bleach activators, suds boosters or suds suppressors, anti-tarnish and anti-corrosion agents, soil suspending agents, soil release agents, germicides, pH adjusting agents, nonbuilder alkalinity sources, chelating agents, smectite clays, enzymes, enzyme-stabilizing agents and perfumes. See U.S. Pat. No. 3,936,537, issued Feb. 3, 1976 to Baskerville, Jr. et al., incorporated herein by reference.
Bleaching agents and activators are described in U.S. Pat. No. 4,412,934, Chung et al., issued Nov. 1, 1983, and in U.S. Pat. No. 4,483,781, Hartman, issued Nov. 20, 1984, both of which are incorporated herein by reference. Chelating agents are also described in U.S. Pat. No. 4,663,071, Bush et al., from Column 17, line 54 through Column 18, line 68, incorporated herein by reference. Suds modifiers are also optional ingredients and are described in U.S. Pat. No. 3,933,672, issued Jan. 20, 1976 to Bartoletta et al., and U.S. Pat. No. 4,136,045, issued Jan. 23, 1979 to Gault et al., both incorporated herein by reference.
Suitable smectite clays for use herein are described in U.S. Pat. No. 4,762,645, Tucker et al., issued Aug. 9, 1988, Column 6, line 3 through Column 7, line 24, incorporated herein by reference. Suitable additional detergency builders for use herein are enumerated in the Baskerville patent, Column 13, line 54 through Column 16, line 16, and in U.S. Pat. No. 4,663,071, Bush et al., issued May 5, 1987, both incorporated herein by reference.
The following examples are presented for illustrative purposes only and are not to be construed as limiting the scope of the appended claims in any way.